Substituted catechol salts of benzotriazoles or phenylhydrazines

ABSTRACT

THE INVENTION IS NOVEL COMPOUND WHICH MAY BE PRODUCED BY REACTION OF A SUBSTUTUTED CATECHOL WITH EITHER PHENYLHYDRAZINE OR A SUBSTUTUTED PHENYLHYDRAZINE OR WITH BENZOTRIAZOLE OR A SUBSTUTUTED BENZOTRIAZOLE. THE REACTION MAY BE CARRIED OUT IN AN INERT SOLVENT, SUCH AS A HYDROCARBON. THE COMPOUNDS ARE USEFUL AS ANTIOXIDANTS IN LUBRICANT COMPOSITIONS.

United States Patent 3,592,820 SUBSTITUTED CATECHOL SALTS 0F BENZO- TRIAZOLES 0R PHENYLHYDRAZINES Keith Coupland, Hornsea, and John Pennington, Willerby, England, assignors to BP Chemicals (U.K.) Limited, formerly known as Distillers Chemicals and Plastics Limited, London, England No Drawing. Filed Dec. 18, 1967, Ser. No. 691,125 Claims priority, application Great Britain, Dec. 24, 1966,

Int. Cl. C07c 109/04; C07d 55/04 11.5. CI. 260-308B Claims ABSTRACT OF THE DISCLOSURE The invention is novel compound which may be produced by reaction of a substituted catechol with either phenylhydrazine or a substituted phenylhydrazine or with benzotriazole or a substituted benzotriazole. The reaction may be carried out in an inert solvent, such as a hydrocarbon. The compounds are useful as antioxidants in lubricant compositions.

where X is a cation of formula where R is an alkyl, aralkyl, alkenyl or aralkenyl radical, and R R and R are hydrogen, halo or alkyl, aralkyl,

alkenyl,- aralkenyl, or alkoxyl radicals.

R is preferably a bulky substituent in which the carbon atom immediately adjacent to the aromatic ring is attached directly to 3 or 4 carbon atoms, such as a tert butyl, alpha-methylbenzyl or alpha, alpha-dimethylbenzyl radical, and may suitably contain from 4 to 12 carbon atoms. R may be, for example, a methyl or ethyl radical or the same as R and preferably contains from 1 to 12 carbon atoms.

The novel compound may be made by the reaction of a substituted catechol with either benzotriazole or a substituted benzotriazole, or with phenylhydrazine or a substituted phenylhydrazine. The reaction may be carried out ice at room temperature in an inert solvent such as hydrocarbon, for example benzene or n-heptane.

The novel compounds find use as antioxidants in lubricant compositions. The lubricant base can be, for example, a hydrocarbon oil of the type used in crankcase oil formulations for internal combustion engines. Alternatively, the lubricant base can be a synthetic lubricant, for example an alkyl ester of an aliphatic dicarboxylic acid, such as dioctyl sebacate, or a base which is described and claimed in British patent specification 1,036,692.

The lubricant compositions may also contain additives such as viscosity index improvers, pour point depressants, dispersants and detergents.

The invention is further illustrated in the following examples.

EXAMPLE 1 22.2 gm. of 3,5:ditert butyl catechol was dissolved in n-heptane and 10.8 g., of phenyl hydrazine added with constant stirring. A white crystalline precipitate rapidly formed and was isolated by filtration. The structure of the product, established by molecular weight, infra-red spectroscopy and chemical analysis is:

tBu OH tBu EXAMPLE 2 22.2 gm. of 3,5:ditert butyl catechol was dissolved in n-heptane, and a saturated solution of 11.9 gm. of benzotriazole in benzene added. The mixture was set aside, and gave an yield of White crystals. The structure of the product is believed to be tBu 6 tB u EXAMPLE 3 35 gm. of 3:5 bis(alpha,alpha-dimethyl benzyl)catechol was dissolved in a mixture of n-heptane and benzene and 11 gm. of phenyl hydrazine added with stirring. A finely divided white precipitate was isolated in high yield and identified as:

P{ /Me C\ O H Me I Ph Me EXAMPLE 4 TABLE 1 Properties of the oxidised materials NHaNH- R4 Corro- Copper sion corro- Fluid Fluid Add tinhibi- (5101'; viscosity weight 1 ve or, permg. increase loss, 1 Base fluid (percent) cent my) percent percent where R is an alkyl or aralkyl radical of 4-12 carbon I N 0 0 260 1 1 atoms, and R R and R are hydrogen, halogen or i 0116.-." one.--

Trimethylolpw Materi d 1.60 130 H alkyl, aralkyl or alkoxyl radicals of 1-12 carbon atoms. pane tricaprylate A (0.5). q 17 2. Compounds according to claim 1 wherein R is a (TMPTC) i radical in which the carbon atom immediately adjacent 0. 5) to the aromatic rim is attached direct Material ..do 0.01 280 17.2 atoms g 1y to 3 or 4 carbon Ex.2 (0.5). 3. A process for making compounds claimed in claim 1 which comprises reacting a compound of the formula OH EXAMPLE 5 l R1 OH Table 2 below demonstrates the copper corroding properties of the product of Example 3, in comparison with additive A and benzotriazole, when subjected to the test described in Example 4. R

TABLE 2 Additives, percent Used blend properties Benzo- Copper corrosion Fluid triazole dibutyl cete- 100 F., Benzochol Wt. viscosity trlaconden- Loss Loss loss, increase, Varnish Base fluid A role sate mg. (mg./ percent percent (mg.)

'IMPTC 0-5 0-1 17-2 280 0-157 TMPTC (66%) 33% cyclohex- 0-5 Nil 11-1 145 27 amine 2,2,6,6, tetra (beta- 0-5 0-1 l-Q 0-2 6-6 03 0-036 propionate n-butyl ester).

EXAMPLE 6 with a compound of the formula The test described above at Example 4 was also carried out in the presence of the antioxidants N-acetyl-Z-hydroxy-3z5 ditert butyl-4'-methyl diphenylamine (B) and 40 N N-benzoyl-2-hydroxy-3:S-ditert butyl-4-methyl diphenylamine (C). The copper corroding properties of the prod not of Example 2 in the presence of additive A and additive B, in comparison with benzotriazole, a known copper corrosion inhibitor, were examined and are reported in Table 3.

The lubricant base fluid used in these tests comprised. 33% cyclohexanone 2,2,6,6 beta-propionate n-butyl ester in an inert solvent.

4. A compound according to claim 1, wherein R and R are tertiary butyl.

5. A compound according to claim 1, wherein R and R are alpha,alpha-dimethylbenzyl.

6. A compound of the formula with 66% TMPTC.

TABLE 3 Copper corrosion Fluid X Antioxidant, Corrosion inhibitor, imgJ loss, percent percent curpercent I Additive B (0.5) 2. 70 as R2 Additive c (0.5) 3.80 5.20 Additive B (0.5) Product of Example 0.01 4.00

4 2 .5.). where X is a cation of the formula 4 Additive c (0.5) o 0.04 e. 5 Additive B (0.5).. Benzotriazole (0.1) 0.16 12.1 0 Additive c (0.5) o 2. 40 3.50 7 Additive B (0.5).. Benzotriazole (0.2)-.-- 0.38 13.9 HzltI 00 l R We claim: N 1. Compounds of the formula: N

y where R is an alkyl or aralkyl radical of 4-12 carbon atoms, and R and R are hydrogen, halogen or alkyl R1 b0 i aralkyl or alkoxy radicals of 1-12 carbon atoms. \/l 7. A compound of the formula l R2 on where X is a cation of formula 70 R1 0 H I I x R3 N\ I 9. A compound according to claim 7, wherein R and R are tertiary butyl, and R is hydrogen. 10. A compound according to claim 7, wherein R H3NNH- and R are alpha,alpha-dimethylbenzyl, and R is hy- 5 drogen.

where X is a cation of the formula References Cited Ciusa et al.: Chem. Abstracts, v01. 5, p. 1744 (1911).

where R is an alkyl or aralkyl radical of 4-12 carbon atoms, and R and R are hydrogen, halOgen or alkyl, 10 ALTON ROLLINS Primary Examiner aralkyl or alkoxy radicals of 1-12 carbon atoms.

8. A compound according to claim 6, wherein R and R are tertiary butyl, and R is hydrogen.

U.S. C1. X.R. 

